ORGANOMETALIC COMPOUNDS (2)

Author: MARTÍNEZ TEJERO MARÍA ABIGAIL.
Year: 2005.
University: BURGOS [www.ubu.es].
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: At work we present the synthesis, structural characterization and study of the reactivity of new complexes monkey, bi and tetranucleares of palladium (II) and a new complex of platinum (II). Likewise, the memory summarizes a systematic study of the non-covalent interactions in solid state and in solution parala most of the compounds mentioned. Mononuclear were synthesized complexes with ligands hidrazona ortometalados formula [Pd (C6H4-N (R) - N = C (CH3) -C5H4N) (? 1-L)] n (where: R = H, CH3;? 1 - L = Cl, 2,6-dimetilpiridina, PMe2Ph, PMePh2, dppm (Ar-NNN-Ar) - (being Ar = 4 - (CH3O) C6H4, 4 - (CH3) C6H4, C6H5, 4-F-C6H4, C6F5)), which were studied in solid state and in solution: The complex binucleares type [Pd2 (C6H4-N (R) - N = C (CH3) -C5H4-N (R ') - N = C ( CH3) -C5H4N) (u-LL)] n (u-LL = dppm, dppe (Ar-NNN-Ar) - (where Ar = 4 - (CH3) C6H4, 4-F-C66H4, C6F5); R and R 'can be: H and / or CH3). In cases where R = R ': get complex binucleares with two equal halves, and when R? R ': species binucleares with two different halves. The complex of this kind allow us to draw correlations between the NMR spectra of 1H and pp interactions present in solution. Moreover, it was possible desprontonar the NH group of igando hidrazona metalado in those complexes prepared to obtain species zwiteriónicas, color very unusual in compounds Pd (II) such as green, blue or violet very intense. These compounds could be characterized in solution by NMR. On the other hand, have summarized the diastereomers (?, S, S) and (?, S, S) complex [(Pd (C6H4-N = N-Ph)) 2 (u - (S) - (OL ( CH (CH3) Br) N-Tol)) 2)], which could be separated by chromatography. Only got co-cristalizar a mixture of both isomers and resolve its structure through diffraction RX. We also extracted cristlaes suitable for study by diffraction Rx complex described by Cope and Siekman in 1965 [(Pd (C6H4-N = N-Ph)) 2 (u-Cl) 2]. Lastly, have been synthesized and characterized complex tetranucleares of general formula [Pd4 (u-LL) 4 (uX) 4] = (where LL (Ar-NNN-AR) - or (Ar-NC (CH3) N-Ar) - (Ar = p-Tol, 4-F-C6H4), and being X = Cl, Br, l). The electrochemical behavior for the complex with ligand NC (CH3) N "turned out to be very different from that observed for the species" NNN ". This means that it is distinct from one another molecular topologies. The ligands hidrazona and azobenceno ortometalados to Pd (II) form p extensive systems that seem to favor the formation of Interaction pp. These interactions, together with the hydrogen bond, have been studied in solid state (through diffraction RX) and dissolution (by espectrosocopia NMR 1H).

Author: MASLLORENS LLINÀS ESTER.
Year: 2005.
University: GIRONA [www.udg.es].
Place of defense: UNIVERSIDAD DE GIRONA.
Place of preparation: UNIVERSITAT DE GIRONA.

Author: MARTÍN POSADAS CRISTINA ISABEL.
Year: 2005.
University: SEVILLA [www.us.es].
Place of defense: CENTRO NACIONAL DE ACELERADORES.
Place of preparation: INSTITUTO DE INVESTIGACIONES QUÍMICAS.

Summary: In this Doctoral Thesis have been carried out and activation processes coupling of olefins, alquinos deficient in electrons (acetilendicarboxilato Dimethyl, propiolato methyl) and aliphatic aldehydes (CH3CHO, (CH3) 3CCHO) and aromatic (p-C6H4-Ome, p C6H4-Me, p-C6H4-NO2) through complex iridium (I) 18 electrons TpMe2lr (C2H4) 2 (TpMe2; hidrotris (3,5-dimetilpirazolilborato). These processes have allowed synthesize new organometallic complexes in its Most have been isolated and characterized. Adicinalmente during this investigaicón has been made: Studies mecanicistas about the formation of one of the complexes synthesized, which have isolated intermediate type iridaciclopentadienos or iridacicloheptadienos (seen as key intermediates in the ciclotrimerización of alquinos catalyzed by transition metals) and alcoxiiridafuranos. Comparative studies of the reactivity of the complexes irido (R) TpMe2lr (C2H4) 2 and TpMe2lr (DMAD) (C2H4) (one of the new compounds synthesized in this Doctoral Thesis) vs. the alquinos acetilendicarboxilato Dimethyl and propiolato methyl. reactivity studies of hidruros-iridafuranos synthesized from TpMe2lr (C2H4) 2, alquinos (acetilendicarboxilato Dimethyl, propiolato methyl) and aliphatic aldehydes (CH3CHO, (CH3) 3CCHO) and aromatics (p-C6H4-Ome, p-C6H4-NO2) versus acetonitrile, otileno, alquino acetilendicarboxilato Dimethyl and hydrogen.

Author: ZARANDONA PORRAS MALKOA.
Year: 2005.
University: PAÍS VASCO [www.ehu.es].
Place of defense: FACULTAD DE QUÍMICAS DE SAN SEBASTIÁN DE LA UPV-EHU.
Place of preparation: FACULTAD DE QUÍMICA DE SAN SEBASTIÁN DE LA UPV-EHU.

Summary: The present report describes the reactivity of o - (difenilfosfino) benzaldehido (PCHO) with complex diolefínicos of rhodium (I) containing ligands N-dadores. Particular attention has been paid to the influence they can have on the course of the different reactions, aspects such as the nature of the ligands diolefínicos and the N-dadores, estequiometría of reactions, especially regarding Rh: PCHO, and reaction medium. The compounds obtained have been characterized by elemental analysis, electrical conductivity, espectroscopias infrared and magnetic resonance multinuclear, mass spectrometry and X-ray diffraction The complex diolefínicos of rhodium (I) with ligands N-dadores react with PCHO and form of preferred reaction is always the adiciónoxidativa the aldehyde group of ligand. When diolefina is 1,5-ciclooctadieno occurs moved generating acilhidruro-complejos of rhodium (III). The presence of a second molecule PCHO leads to the formation of different types of complexes for the different reactivity that may experience the second group fosfina-aldehido. When the ligand N-dador contains an amino group coordinated rhodium, the preferred reaction is the formation of new links carbono-nitrógeno, imine formation of a group or a group hemiaminal, depending on the ligand nitrogen used. On the other hand, when there is no coordinated amino groups, the aldehyde group undergoes formal incorporation of hydrogen, giving complexes diacilo, depending on the reaction conditions. When diolefina is norbornadieno takes place oxidative addition of aldehyde assisted by the formation of chelate followed by a transfer of Hydrogen norbornadieno giving acil-alquil complexes of rhodium (III) nortriciclil or norbornenil. These derivatives are isomers which are obtained selectively depending on the solvent used.

Author: MARÍN CARBALLA MARÍA DEL CARMEN.
Year: 2005.
University: VIGO [www.uvigo.es].
Place of defense: FACULTAD DE QUÍMICA UNIVERSIDAD DE VIGO.
Place of preparation: FACULTAD DE QUÍMICA - UNIVERSIDAD DE VIGO.

Summary: The thesis deals with the synthesis and caracterizaicón new compounds kingdom with ligands dadodres phosphorus capable of stabilizing ligands derived from nitrogen, such as: diaceno, hydrazine, hydroxylamine and imina. These compounds are of great interest because it among their potential applications include help to understand the molecular mechanism by which some microorganisms in nature reduce atmospheric nitrogen to ammonia, in conditions much lighter than those used by men. The development of the thesis has been carried out from targets and a methodological approach clear and well structured and has been undertaken with a remarkable skill and knowledge of the experimental techniques common in a laboratory chemistry Organometálica, at all times the scientific method and with strict discipline. The characterization of all the compounds synthesized was carried out through a variety of techniques such as IR spectroscopy, NMR, elemental analysis, X-ray diffraction of monocristal and measures conductivity in solution. These techniques have been used with great effectiveness, demonstrating an important theoretical and practical knowledge both of them. The results and conclusions are relevant for their novelty and contribution to the field of study of Inorganic Chemistry.

Author: LAFUENTE GIMENO MARÍA ESPERANZA.
Year: 2005.
University: ZARAGOZA [www.unizar.es].
Place of defense: INSTITUTO DE CARBOQUÍMICA.
Place of preparation: UNIVERSIDAD DE ZARAGOZA.

Summary: The enormous expectations generated by the properties of materials at the nano-scale is motivating that nanotechnology will become one of the priority research topics throughout the world. Within this multidisciplinary science, which is expected to revolutionize the future technology of this century, are framed carbon nanotubes (CNTs), some materials with some surprising properties that have attracted enormous expectations. In this paper deals with the preparation of composite materials of SWNTs and MWNTs with organic molecules through different procedures including the funcionalización chemistry of SWNTs to improve dispersion and adherence to the matrix. Also addressing the preparation of composite materials CNT / metals for use in catalysis, and hydrogen storage gas sensors. The synthesis and investigation of composite materials based on polymeric matrix and carbon nanotubes are now matters of great theoretical and practical interest in the field of materials science. From the perspective of composite materials, carbon nanotubes can be ideal for reinforcing materials polymeric matrix due to their small size, high modulus of Young in the direction of the axis of nanotubes, and high mechanical strength. The quality of composite materials depends on the dispersion in the polymer matrix, and adherence of carbon nanotubes with the matrix. His insolubility and poor compatibility with the polymer dispersion makes the uniform of CNTs in the polymer matrix very difficult. Thus, the resulting composite materials present lack of uniformity and not reach the desired properties. To overcome this problem, the chemical modification of the surface of CNTs is regarded as the best method to improve the solubility of the material and its compatibility with the polymer matrix. The chemical funcionalización divided bundles of SWNTs and increases the contact surface of the nanotubes to improve the union and interfacial charge transfer in composite materials. Among all drivers polymers, polianilina (PANI) has attained great importance because of their relatively easy processability, electrical conductivity when Doped, and environmental stability. On the other hand, the polymer liquid crystals termotrópicos (LCPs), among them the poliazometinas have seen a growing interest because of the excellent thermal and mechanical properties of the products obtained from their mergers anisotrópicas. In addition, poliazometinas exhibit good thermal stability and resistance environmental, and materials are promising for applications optoelectrónicas and photonics. For these reasons, have chosen these two polymers, polianilina and poliazometina, for the preparation of composite materials from SWNTs funcionalizados, and achieve an effective interaction between the carbon nanotubes and the matrix used to seek significant improvements in the conductive properties, Machinery, electronic and optical connection to the array of departure and for composite materials prepared CNTs without funcionalizar. As for the composite materials of CNTs with metals in heterogeneous catalysis carbon materials have been widely used to disperse and stabilize metal particles. The catalytic properties of these systems are known to depend largely on the support interaction carbon / metal particles. The carbon materials, activated carbons, carbon fiber and carbon nanotubes have been extensively studied for hydrogen storage, as carriers electrocatalíticos for fuel cells as well as hydrogen sensors. The deposition of metal on the carbon material is aimed at increasing the uptake of hydrogen by combining quimisorción with fisisorción. Metals such as Pt or Pd can increase intrinsic sorption capacity of the supports of carbon through the effect called "spillover". With the aim of increasing the storage capacity of hydrogen by means fisisorción direct hydrogen gas 8 on l 57b you nanotubes have been prepared several samples of SWNTs containing nanoparticles of Pd and Pt. In our case, Pd particles have been deposited on SWNTs using a solid-state reaction not previously used in the deposition of metals leading to materials with good dispersion of nanoparticles. Following the same reaction in the solid state in the case of Pd have been prepared samples SWNTs with nanoparticles deposited Pt. The purpose of this study was to verify some of the potential applications of CNTs through the preparation of carbon nanotubes functional for application in the field of catalysis, sensors, hydrogen storage materials and organic matrix composites.

Author: ARNANZ LARA AVELINA.
Year: 2005.
University: AUTÓNOMA DE MADRID [www.uam.es].
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: DEPARTAMENTO DE QUÍMICA INORGÁNICA. FACULTAD DE CIENCIAS, UNVIERSIDAD AUTÓNOMA DE MADRID.

Summary: Currently, the search for molecular systems able to communicate effectively electronic effects between two or more remote sites is a priority area for research, especially as a result of interest in the development of molecular electronics. Therefore, many works have been focused on securing stable material with several metal centers submit an electronic communication between the same variable depending on the nature of the chains functional bridge and the identity of the redox centers. Here, in this report, are synthesized and characterized complexes containing units Co2 (CO) 6 and CO2 (CO) 4 (LL) (LL = ligand bidentado 1,3-fosfina) as centers electroquímicamente assets, interconnected with each other through the ligands organic 2,5-2,4-, 2.3-and 3,4-bis (trimetilsililentinil) thiophene, demonstrating through electrochemical conducted, which have electronic communication between the metal centers, in varying degrees in Depending on the nature of spacer and the substituents on the units dcioalto. Moreover, because of the great versatility submitted by Clusters trinucleares of osmium face units alquino in this report, but began studying the behavior of the previously synthesized organometallic complexes, which contain groups alquino conjuntados and free, with the cluster trimetálico of osmium Os3 (CO) 11 (MeCN), demonstrating through electrochemical study, one of the complex heterometálicos Co. / Os (coordination linear mode), which produces a significant increase in the degree of electronic communication with regarding the composite analog homometálico Co / Co.

Author: MAS MARZA ELENA.
Year: 2006.
University: JAUME I DE CASTELLON [www.uji.es].
Place of defense: E.S.DE TECNO.Y CIE. EXPERIMENTALES.
Place of preparation: E.S.DE TECNO.Y CIE. EXPERIMENTALES.

Summary: N-Heterocyclic carbene ligands (NHC), first coordinated to a metal center by Ãfele and Wanzlick in 1968 and later isolated in the free state by Arduengo, have emerged as promising ligands for the design of new homogeneous catalysts. N-Heterocyclic carbene ligand One of the main reasons why these ligands have been so widely used in catalyst design during the last decade, is that their steric and electronic properties can be easily modulated, mainly due to their relatively simple preparation and the extraordinary high variety of cheap commercial precursors that can be found from the ordinary chemical suppliers. Polydentate NHC ligands has allowed the preparation of new compounds whose stability is entropically improved by the chelate effect.. Not only chelating bis-NHCs are yielding more stable metal complexes, but they are also providing interesting features that can provide fine tuning of topological properties such as steric hindrance, bite angles, chirality and fluxional behavior. With all this in mind, the present work deals with the study of the coordinative versatility of NHC ligands, by designing new coordination topologies and coordination strategies, and by extending their coordination to early transition metals in high oxidation states. The catalytic activities of the complexes obtained in standard reactions are also described, and the results are compared to other complexes containing other classical ligands.

Author: MONTIEL ARGAIZ MANUEL.
Year: 2006.
University: LA RIOJA [www.unirioja.es].
Place of defense: UNIVERSIDAD DE LA RIOJA.
Place of preparation: CENTRO CIENTÍFICO TECNOLÓGICO UNIVERSIDAD DE LA RIOJA.

Summary: The Doctoral Thesis entitled "Optical and structural interaction Au-Tl and applications synthetic" focuses on the study of interactions between centers of gold (I) and thallium (I), and of the properties to which they can give . First compare the influence of groups perhalofenilaurato (R) in both the optical properties in the structural arrangements and takes place the synthesis of various compounds heteropolinucleares gold and thallium both anionic as neutral, in addition to theoretical calculations included in the that shows the influence of interactions Au   Tl in the luminescence and structure in a state of excited some derivative. In the second part of this paper discussed the reactivity of some of these chains heteropolinucleares versus metal complex. In this respect, these have been used acetilacetonato-derivados of different elements transitional or representative presenting electronic configurations layer closed and in which oxygen atoms can act as a bridge between the metal centers. The new complexes synthesized presents novel structural arrangements, and the study of their optical properties both experimental and theoretical, has deepened at the origin of the luminescence in these kinds of systems. As has been previously noted, thallium centers of this type of polymer chains are able to react with additional ligands, acting first as Lewis acids. Thus, after the synthesis of compounds which have primary amines coordinated Tl were observed changes in color of the solid products in the presence of acetone vapors, which led to more in-depth study of these reactions. Thus, in the latter part of this report deals with the synthesis of complexes with diaminas coordinated thallium and considers its reactivity compared with ketones and dicetonas (both in liquid and gaseous state). The use of diaminas with different lengths of string or with the presence of other groups giving has enabled the synthesis of ligands by reaction with acetylacetone, more quickly than by traditional methods. Finally, these complexes have been characterized structurally and has conducted a study of its optical properties.

Author: Barquero Almagro Natalia.
Year: 2006.
University: MURCIA [www.um.es].
Place of defense: Facultad de Química.
Place of preparation: Facultad de Química.

Summary: This thesis consists of three chapters: the first one describes the synthesis and characterization of a new family of alquinil complex rhodium (I) with phosphine ligands dieno and by reaction of fluorine with alquinos terminal complex in the presence of a base. It has studied the activity of these fluorine and alquinil complex rhodium (I) as a catalyst for the polymerization of fenilacetileno observed that present a high catalytic activity and lead to polifenilacetilenos estereorregulares with configuration cis-transoidal. Finally, we have summarized the first poliacetilenos with substituents bipiridina by polymerization catalyzed by complexes of rhodium (I) of the 5-etinil-2, 2'-bipiridina or copolymerization catalysed by rhodium complexes (I) of the 5-etinil- 2.2 '- bipiridina with arilacetilenos. By the reaction of poly (5-etinil-2, 2'-bipiridina) with the corresponding metal precursors were obtained poliacetilenos with complex tetracarbonilbipiridina molybdenum (I) and tris (bipiridina) ruthenium (II) attached to the chain of conjugated polymer. The second chapter first describes the synthesis, characterization and structural study fotofísico of a new series of alquinil complex of gold (I) possessing groups 2.2 '-bipiridilo (bpy) and 2.2': 6.2 ''- terpiridilo (tpy). There have been ionization equilibrium in some of the alquinil complexes prepared to give the cation salts which is a cluster trinuclear and anion is the complex bis (2 - (2.2 '-bipiridin-5-il) ethinyl) aurato (I ). The alquinil complex of gold (I) are prepared luminescent at room temperature in solution and solid state. For reaction of alquinil complex cation with the iron (II) complexes heteronucleares result form the coordination of three groups bpy or two groups terpy to iron, one of which presents an interesting structure type helicato. There have been also alquinil complex dinucleares gold and molybdenum or tungsten, by reaction of ethinyl bipiridinas where the group bpy is coordinated with molybdenum or tungsten complex type acetilacetonato triarilfosfina gold (I). It has been observed that, when coordinated groups bpy or tpy to iron and molybdenum, there is the extinction of the fosforescencia originated in the group oro-etinilbipiridina, with weak fluorescence in complexes of iron or intense fosforescencia located in the group molibdeno-bipiridina , in the compound of molybdenum. The third chapter presents the synthesis of a new difosfina funcionalizada with a group etinilo. It has obtained a family of complex where the new difosfina is coordinated through the phosphorus atoms. However, there has been gained in the complex to be coordinated through the group alquinilo. Nor has his place in the presence of catalytic polymerization of rhodium (I).

Author: VILLA BOLARÍN MARÍA DOLORES.
Year: 2006.
University: MURCIA [www.um.es].
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: HE HAS MADE THE SUMMARY, Characterization (THROUGH DETERMINATIONS ANALYTICAL, ESPECTROSCÓPICAS And DIFRACCIÓN OF X-RAY), AS WELL AS THE STUDY OF INTERACTION WITH DNA (POR DICROÍSMO CIRCULAR, ELECTROFORESIS, GEL FOR AGAROSA And MICROSCOPY OF FORCES ATÓMICAS) NEW COMPLEX ORGANOMETÁLICOS ANTITUMORALES OF PALADIO (II) AND PLATINUM (II) WITH LIGANDOS NUCLEOBASES MODEL, SUCH AS METILCITOSINA, METILTIMINA, METILURACILO, ALQUILGUANINAS And METILHIPOXANTINA AND LIGANDOS TRIAZOLOPIRIMIDINAS. IN PURSUIT OF LIGANDOS THAT ARE CAPACES OF TRANSPORT THE METALODROGA MORE SPECIFICALLY TO CELL CANCERÍGENA, BE USED, IN ADDITION, ESTEROIDES RESULTING FROM THE TESTOSTERONA. ALSO BE CONDUCTED TESTS CITOTÓXICOS OF NEW COMPLEX ORGANOMETÁLICOS OF PLATINUM (II) IN THE LINE PHONES HL60 (LEUKEMIA HUMAN) and T47D (BREAST CANCER).

Author: LARRAZ DUASO MARÍA DEL CARMEN.
Year: 2006.
University: ZARAGOZA [www.unizar.es].
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: It describes the synthesis of new derivatives of gold (I), (III) gold, silver or copper with different ligands Phosphine heterofuncional type (PN) = PPh2py, PPh2CH2CH2py or PPhpy2, obtaining complexes with different nuclearidad yen that the center presents cash several ways of coordinating these ligands. The ánalisis structural derivatives homonucleares gold (I) shows the presence of interactions aurofílicas. Using these derivatives products as a starting point and building on the vacant coordinativa of pyridine nitrogen of the groups have prepared a large number of new complexes, coordination of different metal centers, as Ag (I), Cu (I), Rh (I) , Ir (I), Pd (II) and Pt (II), and in different relationships estequiométricas. So, there are a variety of situations that present structural interactions aurofílicas and heterometálicas, which contributes to the stabilization of these molecules. Another part of this work has been devoted to the preparation of new derivatives with ligands tiolato (L = SC6F5, (2? COOHC5H3NS-) (S3C3N3) (4-CH3-1 ,2-S2C6H3), or (Squin)) selenolato (L = (SePh)) and different ways. In some cases we have studied the reactivity of these metal complexes with other centers in order to obtain derivatives increased nuclearidadhomo- or heteronucleares. We have developed new derivatives calcogenuro type [E (AuP-N) n] n + (E = 0, S, Se, n = 2, 3) and (PN) = PPh2py or PPh2CH2CH2py, by reaction with Ag (I ), Cu (I) and Au (III) allow the synthesis of mixed species polynuclear. Importantly, the vast majority of derivatives described in this report show luminescence, which has been studied in this work. Of particular interest is the intense luminescence presenting derivatives calcogenuro, which varies greatly depending on the calcogenuro bridge energy used. This luminescence is due to transfer cargo LM (LMCT) and it is important the contribution of links heterometálicos.

Author: MARTINEZ CABALLERO MARIA EMILIA.
Year: 2006.
University: CASTILLA-LA MANCHA [www.uclm.es].
Place of defense: FACULTAD DE LETRAS DE CIUDAD REAL.
Place of preparation: FACULTAD DE CIENCIAS QUIMICAS DE CIUDAD REAL.

Summary: Currently, there is a growing interest in the development of Chemical Organometálica and coordination of the so-called "post-metalocenos" for both metals from major groups and for the transition. This development has been driven primarily by new needs that arise, for example in the development of new catalytic processes, design of new materials, and so on. Our research group has extensive experience in the design of new ligands, in particular type "heteroescorpionato" and its coordination of transition metals, especially in the group 4 and 5. The ligands heteroescorpionato used are derived from bis (pirazol-1-il) methane, funcionalizados with an anionic group in carbon metínico bridge to the two rings pyrazole. It allows you to modify the properties of these ligands and metal to force the center to be coordinated to take certain geometries that facilitate access of other ligands. This report has been structured as a general introduction, which makes a bibliographic review of the background and gives most important aspects related to this subject, and in four chapters that contains his work. Each chapter has tried independently by each of them presents the discussion of results, the result of research and development of a description of the experimental processes conducted. It also includes a section of conclusions, showing the most relevant results of this work. Finally, it contains an annex data cristalográficos of compounds characterized by diffraction rayos-Xy a section of literature where appear citations consulted in the creation of this report. In the first chapter of the report, has developed the synthesis and characterization of new complexes dihaluro, alcóxido and amide - Sc and Y, with ligands heteroescorpionato, where the functional group of escorpionato ( "sting"), is a carboxylate group, ditiocarboxilato or etóxido. The second chapter describes the preparation of a series of compounds Sc, Y, La and Nd with ligands hybrid escorpionato / ciclopentadienilo. These ligands have a hybrid ring ciclopentadienilo as "sting". This chapter has completed the synthesis of ligands heteroescorpionato neutral, with a ring ciclopentadieno, which have been used for the synthesis of derivatives of rent Sc and Y by reaction protonolisis. The third chapter has used a new type of ligands heteroescorpionato synthesized recently by our research group, possessing groups acetamidato and tioacetamidato as "sting". These groups can be seen as ligands pseudoalilos. From these ligands have been synthesized and characterized new complexes Sc and Y. Finally, the fourth chapter has conducted a study of the catalytic activity of some of the complexes synthesized in this report, in polymerization processes? -olefinas, Ethylene and styrene, as well as, by opening polymerization processes ring esters are cyclical as lactones, specifically for? -caprolactona to obtain biodegradable polymers.

Author: SANCHEZ MOLINA MARGARITA.
Year: 2006.
University: CASTILLA-LA MANCHA [www.uclm.es].
Place of defense: FACULTAD DE CIENCIAS QUIMICAS (CIUDAD REAL).
Place of preparation: FACULTAD DE CIENCIAS QUIMICAS (CIUDAD REAL).

Summary: Given the great importance it is receiving the design of ligands in the fields of chemistry Organometálica and Coordination, the main objective of this research work has been the synthesis of a wide variety of species precursor ligands heteroescorpionato new generation, and the study of the behavior of such systems heteroescorpionato in coordination with the Transition metal group 4. The ligands heteroescorpionato synthesized are derived from bis (pirazolil) methane, funcionalizados with an anionic group in carbon metínico bridge both pyrazole ring. This group allows modulate the properties of these ligands and metal to force the center to be coordinated to take certain geometries that facilitate access of other ligands. This report has been structured on the basis of a general introduction, which is a review of the record in this matter, and three chapters which collects the work done. Each chapter has tried independently, and each of them presents an introduction, which describes the most important aspects of functional group introduced in the escorpionato, what we call "sting" of the same. Later, a discussion of results, the result of research development, which impacted on the methods of synthesis and particularly in the characterization of the compounds prepared and finally a description of the experimental processes. In the first chapter of this report has synthesized a new type of ligands heteroescorpionato possessing groups acetamidato and tioacetamidato as "sting". These groups can be considered pseudoalilos. From these ligands, describes the development of new complexes Ti, Zr and Hf. The second chapter describes the preparation of the first ligands hybrid escorpionato / ciclopentadienilo. These ligands, as possessing "sting" a ring ciclopentadienilo, can be considered, as well as ligands ciclopentadienilo with a side chain that ends in two rings pyrazole. Have been prepared from derivatives fulveno. Their ability coordinativa has been tested in front of transition metals group 4, which have been prepared and characterized families with different ligands chloride, rent, alcóxido and imido. Some of these families have been the subject of theoretical level DFT, which have yielded valuable information, both the structures and the nature of the links of such ligands to the metal centers to be coordinated. Finally, the third chapter has dealt with the preparation of ligands heteroescorpionato with an alcohol functional group. The synthetic procedure has been based on an addendum nucleófila to carbonyl groups, which leads to obtaining molecules centers estereogénicos that are presented as mixtures racémicas. It has also been prepared following the same route summarizes a ligand enantioméricamente pure a process diastereoselectivo. These ligands have been used in the preparation of different families of compounds coordination Ti and Zr.

Author: MATAS RUIZ INMACULADA.
Year: 2006.
University: SEVILLA [www.us.es].
Place of defense: CENTRO DE INVESTIGACIONES CIENTÍFICAS ISLA DE LA CARTUJA.
Place of preparation: INSTITUTO DE INVESTIGACIONES QUÍMICAS.

Summary: The studies carried out in this Doctoral Thesis have tried to deepen the knowledge of the interaction metal heteroátomo, from a synthetic, structural and reactivity. They have prepared new nickel organometallic complexes stabilized by the ligand dippe, which have, in general, a link nickel and carbon another nickel heteroátomo. The complex Ni (ME) (F) (dippe) reacts quickly with quantities estequiométricas of LiOH, LiOR, LinRR 'to the corresponding hydroxide complexes, alcóxido or amiduro composition Ni (I) (X) (dippe). Complexes hydroxide, alcóxido and tamiduro show a high tendency to suffer decomposition processes. The complex did not have hidrógenos in position beta ligand in relation to the center metal is likely to decompose process through disproportion. In the decomposition of compounds containing hydrogen atoms in this position competes two mechanisms, one similar to that which operates in the thermolysis of the complex without hidrógenos in beta, and the other goes through the process of elimination beta. The decomposition through elimination beta hydrogen complexes alcóxido and amiduro leads to the corresponding complex Ni (0), which maintains coordinated the organic compound is formed (aldheído, ketone or imina). The more stable complexes aldehyde or ketone is probably due the increased capacity aceptora pi these ligands, which is reflected in some of its spectroscopic and structural characteristics. Of the kinetic studies conducted show that the compounds have examined different behavior with respect to elimination beta hydrogen. Thus, while the complex amiduro decompose spontaneously, alcóxidos require the participation of a catalyst, the effect of which may employ an agent inhibited capture radical. The complex hydroxide, alcóxido and amiduro show a high basicity. His reaction with a variety of ketones, esters leads to the corresponding complexes enolato so direct. Because of their greater reactivity, the complex amiduro of pirrolidina proves to be the most appropriate method to develop this synthetic. The nucleofilia of complexes alcóxido and amiduro is reflected in their reactions with heterocumulenos, which originated products of the formal insertion of these molecules in place on the links oxygen nickel or nickel oxide. The proposed structures confirm the preference of nickel atom coordinated by the fragment XC (= Y) through the atom nature softer (lower S O N smaller). The complex enolato derived from both benzaldehyde acetophenone reacts with carbon dioxide to the corresponding compounds addition. The formation of these complex involves the attack nucleófilo the carbon atom of ligand enolato on the central atom of PhCHO or CO2. Both reactions illustrate the characteristic of reactivity complexes enolato, where the center of activity nucleófilica is in a position remote connection to the center cash. Tests conducted with some of the complex preparations shows its potential utility as catalysts in processes of formation of carbon-carbon links condensation aldólica, and the reacicón of transesterificación.

Author: RESA GALVÁN IRENE.
Year: 2006.
University: SEVILLA [www.us.es].
Place of defense: DEPARTAMENTO DE QUÍMICA INORGÁNICA - INSTITUTO DE INVESTIGACIONES QUÍMICAS.
Place of preparation: UNIVERSIDAD DE SEVILLA.

Summary: In this thesis has been prepared new metalocenos zinc and mercury, which cincocenos prepared present a structural different from those found in the literature. It has also led studies on the chemical reactivity of any of these cincocenos obtained from other compounds of zinc in nature semisandwich (C5Me5) ZnR, which were hitherto unknown. It has also prepared the first stable molecular compound containing zinc metal-metal and is therefore a compound of zinc (I), so far unknown to this element. This compound has been studied using very different techniques, both as a structural and spectroscopic studies also free its chemical reactivity. Perhaps with this compound has opened a new door in the chemistry of the elements of group 12, and especially zinc.